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Updated: Jan 13, 2026
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Cercosporin-Photocatalyzed [4+1]- and [4+2]-Annulations of Azoalkenes Under Mild Conditions
Published on: July 17, 2020
Axially Linked Triphyrin(2.1.1)-Metalloporphyrin Dyads: Interplay between Aromatic-Aromatic and Antiaromatic-Aromatic
Anasuya Maji1, Akrti Sharma1, Mangalampalli Ravikanth1
1Department of Chemistry, Indian Institute of Technology Bombay, Powai, Mumbai 400076, India.
New triphyrin-metalloporphyrin dyads were synthesized and characterized. Aromatic-aromatic dyads show potential energy transfer, while antiaromatic-aromatic dyads exhibit unique spectral properties and nonfluorescence.
Area of Science:
- Coordination Chemistry
- Supramolecular Chemistry
- Photochemistry
Background:
- Axially bonded dyads offer unique platforms for studying electronic interactions.
- Triphyrin and metalloporphyrin complexes are versatile building blocks in supramolecular chemistry.
Purpose of the Study:
- To synthesize and characterize novel aromatic-aromatic and antiaromatic-aromatic axially bonded dyads.
- To investigate the electronic interactions and photophysical properties of these dyads.
Main Methods:
- Synthesis via MII-pyridyl "N" interaction.
- Characterization using NMR spectroscopy and X-ray crystallography.
- Absorption, electrochemical, fluorescence, DFT, and TD-DFT studies.
Main Results:
- Stable dyads were synthesized, with structural analysis revealing near-perpendicular orientation of triphyrin to metalloporphyrin.
- NMR studies showed significant upfield shifts, indicating metalloporphyrin ring current effects.
- Electronic interactions were weak, preserving individual component characteristics. Antiaromatic-aromatic dyads displayed unique spectral bands and lower binding constants.
- Aromatic-aromatic dyads showed potential singlet-state energy transfer to ZnP; antiaromatic-aromatic dyads were nonfluorescent.
Conclusions:
- The synthesized dyads are stable and well-defined supramolecular structures.
- Electronic communication between components is weak, but distinct photophysical behaviors were observed.
- DFT/TD-DFT studies support experimental findings, validating the structural and electronic models.
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